HYDROGEN PEROXIDE

6


CHAPTER 1: INTRODUCTION

Hydrogen peroxide (H
2
O
2
) is a very pale blue liquid which appears colorless in a
dilute solution, slightly more viscous than water. It is a weak acid. It has strong
oxidizing properties and is therefore a powerful bleaching agent that is mostly used
for bleaching paper, but has also found use as a disinfectant, as an oxidizer, and as a
propellant for rockets.
As simple as it may seem, the treatment of contaminated waters is as diverse and
complicated as the operations from which it comes. In today's environment, where
merely transferring contaminants from one medium to another is no longer
acceptable, it is no surprise that a powerful oxidizer that looks like water -- in its
appearance, chemical formula and reaction products -- should be so widely used. This
is hydrogen peroxide (H
2
O
2
) -- a powerful yet versatile oxidant that is both safe and
effective.

Fig.1 H
2
O
2
Bonding [2]

1.1 History

In the years following discovery of hydrogen peroxide in laboratory in 1818, four
processes have made the chemical available commercially first to be commercialized
HYDROGEN PEROXIDE
7

was chemistry related to the laboratory discovery route: reacting barium peroxide
with sulfuric acid to produce hydrogen peroxide and barium sulfate.
A few decades after the first commercial process was introduce, electrolytic processes
were developed and placed in operation. Variation of electrolytic routes appeared as
economic improvements and proprietary position were sought. Plants were built in
many locations throughout the world, supplying product to relatively small market
radii until the last of the last of the larger electrolytic plants was shut down in 1983.
The third process to manufacturing hydrogen peroxide is the overwhelmingly
predominant commercial process in use in the 1980s, other processes having been
shut down over a period of years as economics dictated. The widely used process is
based on the non-catalyzed oxidation of alkyl anthrahydroquinone, often commonly
referred to as the quinine process for hydrogen peroxide.
Before further explanation of the quinine process, the fourth commercial process for
producing hydrogen peroxide should be listed. Principal chemistry of this process was
oxidizing iso-propanol to produce hydrogen peroxide (by product) and acetone .The
only plant built with this process operated until 1980, in the era when the advantage
of the quinine process was accelerating, and a number of electrolytic plants were still
operating.
About 50% of the world's production of hydrogen peroxide in 1994 was used for
pulp- and paper-bleaching.
Other major industrial applications for hydrogen peroxide include the manufacture of
sodium percarbonate and sodium perforate, used as mild bleaches in laundry
detergents. It is used in the production of certain organic peroxides such as dibenzoyl
peroxide, used in polymerisation and other chemical processes. Hydrogen peroxide is
also used in the production of epoxides such as propylene oxide.
New industrial and home applications may be developed with the discovery of a
catalytic reaction using powdered precious metal-based catalyst, hydrogen peroxide
and methyl alcohol. A small plastic bottle incorporating these can produce
superheated steam in one to two seconds releasing only CO
2
and high temperature
steam for a variety of purposes.



HYDROGEN PEROXIDE
8


CHAPTER 2: LITERATURE SURVEY

2.1 Reactions

Principal reactions in the quinine process for hydrogen peroxide are as follows:
Oxidation
Hydroquinone + oxygen Quinine + hydrogen peroxide (2.1)
Hydrogenation
Quinone + Hydrogen

Catalyst
Hydroquinone (2.2)

Conditions of a commercial process require that a third reaction group be added to the
oxidation and hydrogenation, namely:
By-product reactions

derived Quinone
ne Hydroquino
Quinone

)
`

by product (2.3)
Quinone- derived by -products can be subdivided into three categories:

1. Adjust by-products which produce hydrogen peroxide in hydrogenation /oxidation
as in equations (2.1) and (2.2). Tetraquinone (Tetrahydroalkylanthraquinone) is the
only adjunct by-product.
2. Regeneration by-products which do not produce hydrogen peroxide and which
may be converted in high yield to useful quinine or tetraquinone. Epoxide is the most
prominent of by-product.
3. Degraded by-products which do not produce hydrogen peroxide and which may
be converted at low yield or not at all to useful quinines.[3]

Paths and mechanisms for by-product reactions are not clearly defined. In some by-
product reactions there may be a reactant such as hydrogen or oxygen in addition to
the organic molecule. In other case, movement of the labile hydrogen may define a by
product. In cases where careful work has been done to isolate and identify quinine-
HYDROGEN PEROXIDE
9

derived by-products in commercial systems, the possibility exists that some
compounds isolated had parentage in quinine-like impurities introduced with
commercial purity raw material quinine.

Oxidation

Hydrogen
ne Tetraquino
Quinone
Oxigen
quinone Tetrahydro
ne Hydroquino
+

+
)
`

peroxide ( 2.4)

Hydrogenation

\
|
+
|
|
.
|
quinone Tetrahydro
ne Hydroquino
Hydrogen
ne Tetraquino
Quninone
Catalyst
(2.5)

By-product Reactions

derived Qunone
ne Tetraquino ne Hydroquino
ne Tetraquino Quinone

)
`

,
,
by-products (2.6)

Heats of reaction are moderately high exothermic for both hydrogenation and
oxidation. [2]












HYDROGEN PEROXIDE
10


2.2 Manufacturers of Hydrogen Peroxide

- Shrenuj Dye-Chem.
Ahmedabad, Gujarat

- Vishal Enterprises.
Chennai, Tamil Nadu

- Pallav chemical & solvent pvt. Ltd.
Mumbai, Maharashtra

- Gujarat Alkali & Chemical Ltd.
Vadodara, Gujarat

- Orbit Texchem Private Ltd.
Surat, Gujarat

- Kor Chem Ltd.
Ankleshwer, Gujarat

- Meru Chem Industries.
Mumbai, Maharashtra

- Dharani Export-Import Services (p) Ltd.
Chennai, Tamil Nadu

- Shakambari Enterprises India Private Ltd.
Nagpur, M.P.




HYDROGEN PEROXIDE
11


CHAPTER 3: PROCESS SELECTION & DESCRIPTION
3.1 Types of Processes
3.1.1 Catalytic H
2
O
2

The more difficult-to-oxidize pollutants may require the H
2
O
2
to be activated with
catalysts such as iron, copper, manganese, or other transition metal compounds. These
catalysts may also be used to speed up H
2
O
2
reactions that may otherwise take hours
or days to complete. H
2
O
2
catalysis may occur either in solution (using soluble
catalysts) or in packed columns (using solid catalysts).[1]
3.1.2 Solution Catalysis
The most commonly used solution catalyst is iron, which when used with H
2
O
2
is
referred to as Fenton's Reagent. The reaction requires a slightly acidic pH and results
in the formation of highly reactive hydroxyl radicals (-OH) which are capable of
degrading most organic pollutants. Another solution catalyst is copper, which is often
used to destroy cyanides. Other metals also show catalytic activity with H
2
O
2
and may
be used to selectively destroy specific pollutants.[1]
3.1.3 Advanced Oxidation Processes (AOP's)
Hydrogen peroxide is manufactured today almost exclusively by the autoxidation of
2-ethyl-9,10-dihydroxyanthracene (C
16
H
14
O
2
) to 2-ethylanthraquinone (C
16
H
12
O
2
) and
hydrogen peroxide using oxygen from the air. In this reaction, the hydroxy groups on
the middle ring of anthracene are deprotonated and are turned into ketones, while two
double bonds are lost from the middle ring and are replaced as C=O double bonds in
the ketone groups. The anthraquinone derivative is then extracted out and reduced
back to the dihydroxy compound using hydrogen gas in the presence of a metal
catalyst. The overall equation for the process is deceptively simple:
H
2
+ O
2
H
2
O
2

HYDROGEN PEROXIDE
12


However the economics of the process depend on effective recycling of the quinone
and extraction solvents, and of the hydrogenation catalyst.[1]
3.2 Selected Process
In the above-mentioned processes the Advanced Oxidation Process is most widely
used at present in the world .this process has the raw materials of Hydrogen, oxygen,
quinone, solvent. This process is selected because it gives high conversion compared
to other processes also raw material is cheaper and easily available in the market
without fluctuations. This process also gives the high purity of product.
Considering the situation of our country & its economy, I would like to select the
above, most widely used process because of the following reasons.
(A) Raw material hydrogen, oxygen, quinine, solvent is available in plenty of quantity
in the market.
(B) Consideration of the application of advanced technology, the high quality of
product is achieved by this process.
(C) It is cheaper process as compared to other processes.
(D) This method of production of Hydrogen peroxide is widely used almost in the
world.[3]

3.2.1 Raw Materials
- Hydrogen
Hydrogen from any of a variety of sources is suitable as a raw material if certain
purity standers are met. Its assay can be well below 100% since the hydrogenation
reaction effectively captures hydrogen values from the feed gas. High assay feed
hydrogen is most commonly used since it is not particularly difficult to achieve,
benefits hydrogenator design to some extend, and minimizes purging non- reactant
gas components from the system. Carbon dioxide and hydrogen are inert in the
hydrogenation reaction and are vented unused.
Hydrogen purity must be very high with respect to carbon monoxide, which is a
virulent poison for palladium catalyst. Contamination by carbon monoxide manifests
itself when its concentration is above 1 ppm. If monoxide concentration rises to

HYDROGEN PEROXIDE
13


several parts per million even briefly, hydrogenation activity declines abruptly.
Catalyst poisoned by carbon monoxide can be restored to activity by restoring feed
hydrogen purity or by the more arduous route of processing catalyst through the
catalyst regeneration cycle.
Sulfur in sulfide from is a hydrogenation catalyst poison but is seldom encountered in
hydrogen sources feasible for the peroxide process.


- Oxygen (Air)
A process air compressor is often considered a process auxiliary rather than a utility.
The compressor feeding raw material air feed to oxidizer is the largest energy user in
the process. Only sufficient air is fed to oxidize all hydroquinone in the oxidation
step, but a moderate excess may be used. An advantageous compressor design allows
for energy consumption turndown commensurate with air rate turndown to keep
energy cost of this unit proportional to hydrogen peroxide production. Air need not be
dessicated or specially cleaned beyond filtering before feeding to the oxidizer.
Standard inter-stage and after coolers on the air compressor suffice to condense
moisture from ambient air. Through de-entrainment of this condensate is necessary. A
fume-free air source is required. A contaminant-free source of air must be regarded
seriously during operation and even in selecting a plant site.

- Quinone
High purity quinone is necessary both for making the initial working solution
inventory and for ongoing makeup. Impurities in feedstock quinone may be of the
degraded by-product class (refer to prior definitions) or of a class which suppresses
hydrogenation activity. If impurities are of the degraded by-product class, they
impose an unnecessary and unwanted load on the purge system for quinone-like by-
products. Metals and chlorides are other impurities which must be prevented from
entering the process via any raw material, particularly quinone.



HYDROGEN PEROXIDE
14

- Solvents Polar solvents are usually specialized raw materials whose quality
factors have been developed by cooperation between the hydrogen peroxide
process company and the solvent manufacturer. High purity is characteristic.
Nonpolar solvents are most often items of commerce whose quality factors are
monitored by the peroxide process company. Several of these solvents are
mixtures of several compounds, so composition is usually not monitored one
the solvent is established as satisfactory for use.


HYDROGEN PEROXIDE
15

Solvent
Purification
72% Hydrogen Peroxide
Product
Anthraquinone+
Solvent
Catalyst
filter
Hydrogenator
Activated
Carbon
Absorber
For Further Treament
Hydrogen
Air or Oxygen Rich Air
O
x
i
d
i
s
e
r
Liquid Liquid
Extractor
Vacuum
Column I
Vacuum
Column II
Make-up
Water Feed
Solvent Recycle
Water
recycle to
Extrator
Thermosyphon
Shell & Tube
Reboiler
Water Recycle
Fig. 3.1 Advanced Oxidation Process
Flow Diagram
Degasser
Reflux
Surge
Drum

HYDROGEN PEROXIDE
1

3.2.2 Basic Reactions

(3.2)


(3.3)

- Overall Reaction:

H
2
+ O
2
H
2
O
2


Hydroquinone reactant in the upper reaction is a product in the lower reaction;
quinine reactant in the lower reaction is a product in the upper reaction. Hydrogen
peroxide is removed from the process chemistry circuit by water extraction.

3.2.3 Working Solution
Chemistry of the system is conducted in an organic solution, commonly called
working solution, which carries the quinine/ hydroquinone through oxidation and
hydrogenation reactions and through the extraction step. The working solution is
contained within the process for the entire life of the plant, being replaced only slowly
by makeup for purges and losses.
Pure quinine, pure hydroquinone, and related species are solids at ambient
temperature, but working solution composition is selected so solubility limits of the
HYDROGEN PEROXIDE
2

solids in the solvents are not exceeded. The organic solution is homogeneous at all
times, with no solid or liquid second phase, at all points in the commercial process.

Working solution is composed of:
Non-polar solvent acting primarily to dissolve the oxidized from of quinine and
tetraquinone.
Polar solvent acting primaritl to dissolved the hydrogenated from of quinine and
tetraquinone.
Quinone/ tetraquinone
Unwanted but unavoidable quinine-related species.

For the quinine member of working solution, processes have used one or a mixture of:
2-Ethyl anthraquinone, 2-Tertiary butyl anthraquinone & 2-Amyl anthraquinone

For the nonpolar solvent member, one or mixture of the following has been used:
Benzene, Mixed alkyl naphthalenes, mixed alkyl benzene, Particular alkyl benzenes

For the polar solvent member, one or a mixture of the following has been used:
Trioctylphosphate, Diisobutyl carbniol, Methyl cyclohexyl acetate, Tetraalkyl urea

In general, by using only one member from each group-quinone, nonpolar solvent-
practical working solutions are formulated. However, mixtures of members from each
group have been used. Hence, there are a large number of operable working solutions.
Even through commercial processes have operated for more than 30 years, a single
dominant working solution composition has not established itself. There are 8-10
principal compositions among those favored by various peroxide manufacturers.
Though two plants may starts with the same composition, process history-excursions
from normal conditions, etc.-influences the working solution composition and the
plants will have different solution compositions after a period of time.




HYDROGEN PEROXIDE
3

- Working Solution Properties:
The process steps described thus far have been commercialized around working
solution which displays the following properties:
1. High solubilitys for the hydrogenated and oxidized states of solids which are
dissolved in the solvents.
2. The solvents resist reaction in the process steps.
3. The organics are soluble in aqueous phase to the lowest possible degree.
4. The solution density is less than that of water. Solutions heavier than the process
aqueous phase are not barred but have not been commercialized.
5. The distribution coefficient of hydrogen peroxide favors the aqueous phase when
in contact with the working solution.

This list could be extended to include the matters of cost, flammability properties, and
toxicity.

3.2.4 Catalyst Options
Another element in Eq. is the hydrogenation catalyst. Palladium as the catalytic
material is widely used. Closely allied to the catalyst and the type of hydrogenator in
which the catalyst is used. Thus, adding to the list of option for practical working
solution are the following choices in the hydrogenation step, where can be used with
most working solutions.

Palladium on catalyst support; slurry catalyst hydrogenator
Palladium on catalyst support; fixed-bed catalyst hydrogenator
Unsupported Palladium; slurry catalyst hydrogenator
Activated alumina is used widely, but not exclusively, for catalyst supports, both for
slurry type and fixed-bed type catalysts.

3.2.5 Process Description
- Oxidation Step
Hydrogen peroxide is first formed in the oxidation step, a gas-liquid contactor.
various designs are in use, usually columns. Air is used as the oxygen source.
HYDROGEN PEROXIDE
4

Economic evaluations as well as safety considerations indicate pure oxygen ism not
competitive with air.
The oxidation step is designed to utilize 70-92% of the oxygen in the incoming air.
Oxygen partial pressure and working solution residence time in the steps are principal
variables which influence design. Residence time usually ranges from 10 to 40 min.
Pressure is usually 1 atm gauge or higher. Where energy costs are high, economics
usually favors the lower end of the pressure range to minimize energy for
compressing the large volume of air. Offsetting lower air compression energy costs at
low pressure are the larger size of the oxidation reactor and the accompanying larer
investment in working solution which is inventoried in reactor.
Another factor affecting oxidation step design is the ratio of anther to tetraquinone in
the working solution. High anthrax/tetra ratio solutions have faster oxidation rates but
slower hydrogenation rates than low anthrax/ tetra solutions. High anthrax/tetra ratio
reduces the total cost of the oxidation step but imposes the tradeoff of less favorable
conditions in the hydrogenation step. The anthrax/tetra ratio changes only a small
amount in the 2-4 h transit time for working solution to circulate once around the
reaction route.
Well over 90% of the hydroquinone fed to oxidation is oxidized in the step. Only
hydroquinone converted to hydrogen peroxide is available for extraction and net
production from the process; any unoxidized hydroquinone passes with the working
solution through the extraction step and into hydrogenation where it joins newly-made
hydroquinone.

- Extraction
Hydrogen peroxide, having been formed by the oxidation reaction and dissolve in the
working solution, passes to the extraction step. Between oxidation and extraction,
hydrogen peroxide concentration in the working solution is in the range 0.8-0.9 wt.%.
in the extractor, a distributed coefficient favorable to the aqueous phase in contact
with the working solution allow hydrogen peroxide to be extracted at concentration
from 25 to 45 wt.% in the extract phase. Efficient extractors deplete the working
solution of more than 95% of its hydrogen peroxide. Any peroxide remaining in the
raffinate working solution is destroyed by subsequent process conditions, thus making
efficient extraction imperative for good overall process economics.
HYDROGEN PEROXIDE
5

Extraction of hydrogen peroxide from the working solution into the aqueous phase is
most commonly done in countercurrent sieves plate liquid-liquid extraction column.
Compact centrifugal extractors may have reached commercial plant installation but
have not found widespread favor, and may have been discontinued in use.
Knowledge of distribution coefficients and mass transfer effects in the working
solution /aqueous system is necessary to design the extraction column. One interesting
aspect of column design is the considerable change in extract phase density from top
to bottom of the column. At the top of the column, extract density is near 1.00 g/ml
(water at operating temperature commonly about 50C). At the bottom of the column,
extract density corresponds to the concentration of Hydrogen peroxide. Raffinate
density does not change appreciably from top to the bottom of the column.
The working solution is usually the dispersed phase in a column-type extractor.
Coalescence of the up-rising working solution droplets is allowed under each plate in
a plate-column design. These strata of coalesced working solution may be 25-100mm
thick, governed by the free area of the particular plate and the density different
between the phases at that region of the column.
Good phase separation is vital for good extractor performance. Mechanical and
chemical means may be used to enhance both phase separation and droplet
coalescence.
At the top of the column where working solution coalesces before leaving the unit, it
is useful to de-entrain as possible from the existing raffinate.
Slurry catalyst may be suspended in the reactor inventory of working solution by
some means of agitation, mechanical or gas.
Hydrogenated working solution leaves the reactor through filters immersed in the
vessel or associated with the main reactor vessel. The principal working solution flow
rate is in the range 30-50 times as large as aqueous flow rate in a typical system.
Conversely, aqueous residence time in a column may be 50-70 times as long as
working solution residence.

- Hydrogenation
Equipment in the hydrogenation step is the most complex in the process. Three
prominent design principles in the hydrogenation are (1) to provide for a high degree
of hydrogen utilization, upwards of 90% and approaching 100%, (2) to retain
HYDROGEN PEROXIDE
6

hydrogenation catalyst within the reaction step, and (3) to be compatible with catalyst
properties.
Hydrogen gas is usually a prominent cost item; hence high yield is sought in making
hydrogen peroxide from this raw material. Hydrogen will be completely consumed by
reaction with quinine in a reaction time of 1-5 min at the usual reaction conditions.
Hence, design is practical to react hydrogen to completion in one pass through the
reactor, leaving little hydrogen to escape. System to recover and recirculate unreacted
hydrogen can be used although they are not necessary on reactors designed to
consume all the gas fed.
Design features of the hydrogenation step must also retain the long-lived catalyst for
ongoing use within the step.
Fixed-bed catalyst reactors inherently retain catalyst within the system while passing
reactors through the catalyst. In this respect, fixed-bed catalyst reactors commend
themselves to the process.
However, with respect to establishing advantageous overall reaction conditions in
working solution systems, fixed-bed hydrogenations have proven complex. Unwanted
side reactions occur in fixed-bed units, and this type of reactor has not found
overwhelming favor despite its deceptive simplicity and appropriateness.
Hydrogenators for slurry-type catalyst can be of many different designs to satisfy the
aforementioned principals which apply to both supported and unsupported catalysts.
In one type of reactor, all the principles can be satisfied in a single vessel
hydrogenator. Hydrogen gas solution and residence time can be sufficient to
reacpurpose of these filters is to retain catalyst within the reactor. Catalyst collected at
the filter medium be released periodically to rejoin the slurry in the hydrogenator.
Some manner of filter reverse flush is commonly used for this purpose.
In other configurations of the hydrogenation step, the reaction function and catalyst-
retaining filtration function may be more distinctly separated than in the single vessel
design.
The hydrogenation must accommodate catalyst properties, particularly with respect to
attrition resistance. Catalyst-retaining filter medium and catalyst filtration properties
are matched so only tracers of catalyst exist from a slurry hydrogenator.


HYDROGEN PEROXIDE
7

3.2.6 Augmenting Process Functions
The three principal process steps in flow sheet oxidation, hydrogenation, must be
augmented by other process functions and supported by a variety of auxiliary
operations.

- Catalyst Particle Barrier
Even though catalyst retention function is design into the hydrogenation step, a
catalyst particle barrier is used in the main working solution stream to assure that no
catalyst particles pass to the oxidation step. Hydrogenation catalyst appearing in the
oxidizer will decompose hydrogen peroxide as soon as the peroxide is created by the
oxidation reaction.
Filtration of the highest efficiency is commonly used for the catalyst particle barrier.
More than one stage of filtration may be used to assure a high degree of integrity to
the barrier.

- Degassing
The working solution entrains and dissolvers air when leaving the gas-liquid
contractor oxidizer, and an air de-entrainment device is installed between the oxidizer
and extractor in the main working solution stream. Entrained gas must be removed
from the working solution so gas bubbles do not enter the liquid-liquid extractor and
disturb interfaces, droplet formation, and droplet coalescence in the extraction
column. Gas bubbles of very small diameter, as well as larger bubbles, must be dealt
with in the design of an effective air de-entrainment device.


- Water Control
Since the working solution is thoroughly contacted with water in the extractor, a water
control function is imposed on the system. The water control function in fig. removes
entrained water from the main working solution stream after it leaves the extractor
and also reduces the water concentration below saturation in the stream. Complete
dessication of the working solution is not necessary in the water control function since
the hydrogenation reaction must have a particular concentration of water in the
HYDROGEN PEROXIDE
8

working solution in order to proceed. The exact role of water in hydrogenation is not
well understood but it is universally recognized to be necessary.
A unit such as a separator is often used to remove entrains water, and second unit,
such as a vacuum flash tank, is used to reduce the water concentration below
saturation in the solution. Operating controls for the temperature and the flash tank
vacuum set the desired water concentration in the working solution and catalyst pair
requires a specific water concentration for optimum hydrogenation; each pair does not
have the same optimum.

- Working Solution Regeneration
Working solution regeneration embodies a number of phenomena. One is to
counteract or in fact reverse unwanted side reaction involving anthrax-and
tetraquinones. In these types of reactions, quinine-related species, which have been
rendered incapable of making hydrogen peroxide, are reverted to useful quinines or
tetraquinones.
Another phenomenon is to dehydrogenate tetraquinone to the anthrax form. Some
processes use a working solution regeneration step which accentuates the
dehydrogenation in order to maintain the composition of the process working solution
inventory high in the anthra form of quinone. Other processes use a regeneration step
in which tetra-to-anthra dehydrogenation is somewhat incidental but which
nonetheless plays a role in setting the anthra/tetra ratio in the working solution
inventory.
Another phenomenon occurring in the regeneration step is unwanted side reactions of
quinone species. Desirable effects of regeneration can predominate over undesirable
effects by choosing suitable operating inventory.
One working solution regeneration treatment is to pass a side-stream of working
solution over a material such as activated alumina which is both absorbent and
selectively catalytic for many chemical reactions. The absorbency function is a fourth
phenomenon occurring in this type of regeneration. Selective absorbency of the
regenerator catalyst removes irreversibly degraded quinone by-products from the
solution.
As shown in fig., the working solution regeneration function is fed a side-stream
which branches from and returns to the main reaction circuit either before or after the
HYDROGEN PEROXIDE
9

hydrogenation step. The four phenomena described previously in this selection occur
to different degrees in the regenerator, depending on the feed source of the working
solution.
Regeneration steps can be used which do not employ a catalyst adsorbent, but these
types of regeneration are used in only a small number of commercial processes.

3.2.7 Auxiliary Operations
- Catalyst Processing
Catalyst processing and preparation may be closely affiliated with the main process or
these operations may be at separate plants or with vendors who specialize in catalysts.
These options are true for fixed-bed and both types of slurry catalysts. The decision is
usually of a make-or-buy nature since the peroxide process inherently neither
mandates close-coupled catalyst processing nor favors off-site processing. Both
reprocessed catalysts taken from the hydrogenator and newly made, never used
catalyst must be considered. All catalysts are stable, and shelf-life is not a problem
when a catalyst is not in use.
Fixed-bed catalyst is usually operated to the end of its useful life, perhaps a few years
with the aid of periodic revivifications in place. The supply of catalyst for changing a
fixed bed can be made in large amounts over a short period of time or in small
amounts which are stockpiled.
Slurry catalysts have an inherent advantage over fixed-bed catalysts in being
amenable to periodic removal and replacement in small amounts in the system. Some
types of slurry catalyst removed from the system are completely remade as if starting
from virgin ingredients. Other slurry catalysts can be regenerated through hundreds of
cycles of use and regeneration without remaking the basic catalyst.
In all cases the valuable palladium or precious metal is diligently pursued to
remake/regenerate into an active catalyst.
Catalyst preparation procedures are closely guarded. Supported palladium catalysts
have precious metal content from 0.3 to 2.0% by weight. The exact supports used,
conditioning of the support, deposition of the palladium, and postdeposition
conditioning figure in making selective catalysts.


HYDROGEN PEROXIDE
10

- Working Solution Makeup
Working solution makeup is another auxiliary unit necessary for ongoing plant
operation. Working solution raw materials-quinone and solvent must be introduced
periodically to maintain steady working solution composition and inventory. Quinone
is dissolved in the solvent or in an aliquot of working solution before being introduced
to the main working solution inventory. The dissolver vessel is usually sized to handle
the one time operation of making the entire system working solution inventory.
However, these facilities are often used to make the entire system inventory just prior
to commissioning the plant.
The makeup quinone solution is usually filtered to insure the cleanest possible state
before introducing it to the main system which has exceptionally efficient filters.
Makeup solvent may be pumped directly to the system through guard filters or
through the filter in the solution makeup equipment.

- Solvent Recovery, Oxidizer Exit Air
Recovering solvent from the oxidizer column exhaust air is necessary for economic
and environmental reasons. The exhaust air is saturated with working solution and
water vapor. The fractional percentage of water concentration in the working solution
contributes a significant amount of vapor to the air exhaust because waters volatility
is substantially greater than the next most volatile component.
Condensers coupled with mist eliminators are used to recover much of the
condensable solvent/water mixture. Low-temperature condensers, again coupled with
mist eliminators, may be used for an adequate final cleanup by running at a
condensate temperature of 2-5C.
Through cleaning of the exhaust air is achieved by absorbing the solvent/water vapor
on activated carbon in a rather straightforward application of adsorbent technology.
When using adsorbent technology it is necessary to recognize the absorbed solvents
low volatility so adequate provision is made for desorption. Exceptionally through de-
entrainment is needed on the absorber feed gas (oxidizer exhaust air) so that working
solution droplets do not reach the adsorbent and progressively diminish the adsorbent
capacity.Solvent recovered from the oxidizer exhaust air is returned to the main body
of the working solution composition.

HYDROGEN PEROXIDE
11

- Oxidizer Air Feed
A process air compressor is often considered a process auxiliary rather than a utility.
The compressor feeding raw material air feed to oxidizer is the largest energy user in
the process. Only sufficient air is fed to oxidize all hydroquinone in the oxidation
step, but a moderate excess may be used. An advantageous compressor design allows
for energy consumption turndown commensurate with air rate turndown to keep
energy coasts of this unit proportional to hydrogen peroxide production. Air need not
be dessicated or specially cleaned beyond filtering before feeding to the oxidizer.
Standard interstage and after coolers on the air compressor suffice to condense
moisture from ambient air. Through de-entrainment of this condensate is necessary. A
fume-free air source is required. A contaminant-free source of air must be regarded
seriously during operation and even in selecting a plant site.

- Water Purification
Deionized water with a resistivity of at least 10^6 /cm is required to feed the
extractor and any other process points to the solutions of hydrogen peroxide.
Sometimes pure water is available from some other process on a common site; more
often the hydrogen peroxide plant creates the need for pure water. Industry stander
water treatments are used to purity the source water to the purity needed in the
peroxide process. The purification sequence is designed to remove virtually all
contaminants, including silica. The water purification system often has a capacity
more than triple the process flow sheet requirement because large amounts of high
purity water are used to wash shipping containers and for other utilitarian purposes.

- Hydrogen Peroxide Product
After synthesis, hydrogen peroxide solution is usually clarified and stabilized, and it is
often concentrated to strengths higher than the extract strength. Clarification to
remove a tracer of haze in the solution is achieved by a combination of filtration and
solvent contact. Stabilization employs certain chemicals, usually inorganic, to
suppress peroxide decomposition created by tracers of contaminants from commercial
processes. Peroxide is usually concentrated in fractional distillation apparatus. [3]


HYDROGEN PEROXIDE
12

CHAPTER 4: PHYSICAL & CHEMICAL PROPERTIES

4.1 Physical Properties

Table 4.1: Properties and Values of Hydrogen Peroxide
PROPERTY VALUE
Melting point /
o
c -0.41
Boiling point /
o
c 150.2
Density at 25
o
c / g ml
-1
1.4425
Viscosity at 20
o
c / mpa s 1.245
Surface tension at 20
o
c / mn m
-1
80.4
Specific conductance at 25
o
c / .cm 4 x 10
-7
Enthalpy of fusion / J g
-1
367.52
Specific heat at 25
o
c / J g
-1
2.628
Heat of vaporization at 25
o
c / J g
-1
1517
Heat of dissociation / kj mol
-1
34.3

4.2 Chemical Properties
H
2
O
2
is one of the most powerful oxidizers known -- stronger than chlorine, chlorine
dioxide, and potassium permanganate. And through catalysis, H
2
O
2
can be converted
into hydroxyl radicals (.OH) with reactivity second only to fluorine.



HYDROGEN PEROXIDE
13

Table 4.2: Various Oxidants and Oxidation Potentials
Oxidant Oxidation potential, V
Fluorine 3.0
Hydroxyl radical 2.8
Ozone 2.1
Hydrogen peroxide 1.8
Potassium permanganate 1.7
Chlorine dioxide 1.5
Chlorine 1.4
Hydrogen peroxide can decompose spontaneously into water and oxygen. It usually
acts as an oxidizing agent, but there are many reactions where it acts as a reducing
agent, releasing oxygen as a by-product. It also readily forms both inorganic and
organic peroxides.
4.2.1 Decomposition
Hydrogen peroxide always decomposes (disproportionate) exothermically into water
and oxygen gas spontaneously:
2 H
2
O
2
2 H
2
O + O
2

This process is very favorable; it has a H
o
of 98.2 kJ mol
1
and a G
o
of
119.2 kJ mol
1
and a S of 70.5 J mol
1
K
1
. The rate of decomposition is
dependent on the temperature and concentration of the peroxide, as well as the pH and
the presence of impurities and stabilizers. Hydrogen peroxide is incompatible with
many substances that catalyze its decomposition, including most of the transition
metals and their compounds. Common catalysts include manganese dioxide, and
silver. The same reaction is catalysed by the enzyme catalase, found in the liver,
whose main function in the body is the removal of toxic byproducts of metabolism
and the reduction of oxidative stress. The decomposition occurs more rapidly in
alkali, so acid is often added as a stabilizer.

HYDROGEN PEROXIDE
14

The liberation of oxygen and energy in the decomposition has dangerous side effects.
Spilling high concentration peroxide on a flammable substance can cause an
immediate fire, which is further fueled by the oxygen released by the decomposing
hydrogen peroxide. High-strength peroxide (also called high-test peroxide or HTP)
must be stored in a suitable, vented container to prevent the buildup of oxygen gas,
which would otherwise lead to the eventual rupture of the container.
In the presence of certain catalysts, such as Fe
2+
or Ti
3+
, the decomposition may take a
different path, with free radicals such as HO- (hydroxyl) and HOO- being formed. A
combination of H
2
O
2
and Fe
2+
is known as Fenton's reagent.
4.2.2 Alkalinity
Hydrogen peroxide is a much weaker base than water, but it can still form adducts
with very strong acids. The super acid HF/SbF
5
forms unstable compounds containing
the [H
3
O
2
]
+
ion. [1,2,4]
























HYDROGEN PEROXIDE
15

CHAPTER 5: MATERIAL BALANCE

Basis: 10000 tons per year of hydrogen peroxide production and 320 working days.

Therefore,
Production of hydrogen peroxide per day =
320
1000 10000x


= 31250 kg/day
So, total requirement of hydrogen peroxide is 31250 kg/day.
Molecular weight of hydrogen peroxide is 34 kg/kg-mole.
So, total requirement of hydrogen peroxide is 919.117 kg-moles.

5.1 Raw Material Requirement

Chemical reactions:
For hydrogenation:

C
14
H
8
O
2
+ H
2
C
14
H
10
O
2

Data:

Molecular weight of Quinone: 208.28 kg/kg-mole
Molecular weight of Hydroquinone: 210.23 kg/kg-mole
Molecular weight of Hydrogen: 2 kg/kg-mole
Molecular weight of Oxygen: 32 kg/kg-mole
Molecular weight of Hydrogen Peroxide: 34 kg/kg-mole

So, requirement of quinone:

210.23 kg of hydroquinone = 208.28 kg of quinone
193226.10 kg of hydroquinone =
210
208.28 x 193226.10

HYDROGEN PEROXIDE
16

= 191433.82 kg of quinone.

= 919.117 kg-mol

Now, requirement of hydrogen;

210.23 kg of hydroquinone = 2 kg of hydrogen

193226.10 kg of hydroquinone =
210.23
2 x 193226.10

= 1838.23 kg of hydrogen.

= 919.115 kg-mol.
For, Oxidation;

C
14
H
10
O
2
+ O
2
C
14
H
8
O
2
+ H
2
O
2

Now, requirement of hydroquinone:

34 kg of hydrogen peroxide = 210.23 kg of hydroquinone

31250 kg of hydrogen peroxide =
34
210.23 x 31250

= 193226.10 kg of hydroquinone.
= 919.117 kg-mol.

Last, requirement of oxygen:
34 kg of hydrogen peroxide = 32 kg of oxygen

31250 kg of hydrogen peroxide =
34
32 x 31250

= 29411.76 kg of oxygen.
= 919.117 kg-mol.

HYDROGEN PEROXIDE
17

5.2 Material Balance over Hydrogenation Unit

Hydrogenator
Hydrogen
1838.23 kg
Hydroquinone
193226.10 kg
Quinone
191433.82 kg


Fig. 5.1 Material Balance over Hydrogenator Unit

Total In = 191433.82 + 1838.23 = 193226.10 kg
Total Out = 193226.10 kg
So, Total In = Total Out

Input in Hydrogenator:
Quinone = 191433.82 kg
Hydrogen = 1838.23 kg

Output from Hydrogenator:
Hydroquinone = 193226.10
(Working solution)
Table 5.1: Material Balance over Hydrogenator

Material In Amount(kg) Material Out Amount(kg)
Quinone 191433.82

Hydroquinone

193226.10

Hydrogen 1838.23


HYDROGEN PEROXIDE
18

5.3 Material Balance over Oxidation Unit

Oxidation Unit
Oxygen
29411.76 kg
Working solution
222637.86 kg
Hydroquinone
193226.10 kg

Fig. 5.2 Material Balance over Oxidation Unit

Total In = 193226.10 + 29411.76 = 222637.86 kg
Total Out = 222637.86 kg
So, Total In = Total Out

Input in Oxidation Unit
Hydroquinone= 193226.10 kg
Oxygen = 29411.76 kg
(Air)

Output from Oxidation Unit
Working solution= 222637.86 kg

Table 5.2: Material Balance over Oxidation Unit

Material In Amount(kg) Material Out Amount(kg)
Hydroquinone 193226.10 Working solution 222637.86
Oxygen 29411.76


HYDROGEN PEROXIDE
19

5.4 Material Balance over Extraction Unit

Extractor
Quinone
191433.82 kg
Working
Solution
222637.86 kg
Hydrogen
peroxide
31250 kg
Water
45.96 kg

Fig. 5.3 Material Balance over Extraction Unit

Total In = 222637.86 + 45.96= 222683.82 kg
Total Out = 31250 + 191433.82 = 222683.82 kg
So, Total In = Total Out

Input in extractor:
Working solution=222637.86 kg
Water =45.96 kg

Output from extractor:
Hydrogen peroxide = 31250 kg
Quinone = 191432.82 kg

Table 5.3: Material Balance over Extractor
Material In Amount(kg) Material Out Amount(kg)
Working Solution 222637.86 Hydrogen peroxide 31250
Water 45.96 Quinone 191433.82




HYDROGEN PEROXIDE
20

CHAPTER 6: THERMODYNAMICS AND REACTION KINETICS

Principal reactions in the quinine process for hydrogen peroxide are as follows:
Hydrogenation
Quinone + Hydrogen

Catalyst
Hydroquinone

C
14
H
8
O
2
+ H
2
C
14
H
8
O
2 [1]
Oxidation
Hydroquinone + oxygen Quinine + hydrogen peroxide

C
14
H
10
O
2
+ O
2
C
14
H
8
O
2
+ H
2
O
2 [2]


The rate equations will be given as follows:

R1

K1 N
C14H8O2
N
H2
(-E1/RT

) [1]
R2 =

K2 N
C14H10O2
N
O2
(-E2/RT

) [2]

Subscripts C
14
H
8
O
2
, H
2
, C
14
H
10
O
2
and O
2
represent Quinone, hydrogen,
hydroquinone and oxygen respectively.




















HYDROGEN PEROXIDE
21

CHAPTER 7: ENERGY BALANCE


Basis: Production of 10000 tons per year of hydrogen peroxide and 320 working days.
Production of hydrogen peroxide is 31250 kg/day.

Normal temperature: 25 C ~ 298K
Base temperature: 29 C ~ 302 K

7.1 Thermodynamic Data

Table 7.1: Thermodynamic data

COMPOUND MOLECULAR
WT.
No. of moles
n
H
f

AT 25C
KJ/MOL
C
P
kg/kmol
K
C
14
H
8
O
2
280.28 919.12 -496.749 47.56
H
2
2 919.115 0 33.94
C
14
H
10
O
2
210.23 919.117 -536.764 25.89
O
2
32 919.117 0 23.70
H
2
O
2
34 919.117 -187.86 67.34
H
2
O 18 2.55 -285.83 33.56

Here,
Cp= (a+bT+cT
2
+dT
3
)

Energy balance with first reaction:

C
14
H
8
O
2
+ H
2
C
14
H
8
O
2

Now,
Heat of reaction= [H
f
(prod.) - H
f
(react)]
= [(-536.764)-(-496.749)]
= -40.015 kJ

HYDROGEN PEROXIDE
22


Heat absorbed or relies by each compound:
For, the first reaction

Reactant (C
14
H
8
O
2
):
Q= nCpT
= (919.12 x 45.56 x 4)
= 167500.428 kJ

Reactant (H
2
):
Q= nCpT
= (919.115 x 33.94 x 4)
= 124779.05 kJ

Product (C
14
H
10
O
2
):
Q= nCpT
= (919.117 x 25.89 x 4)
= 95183.76 kJ

Energy balance with second reaction:

C
14
H
10
O
2
+ O
2
C
14
H
8
O
2
+ H
2
O
2


Now,
Heat of reaction= [H
f
(prod.) - H
f
(react)]
= [{(-496.749) + (-187.86)}] [-536.764]
= -147.845 kJ






HYDROGEN PEROXIDE
23

Heat absorbed or relies by each compound:
For second reaction:

Reactant (C14H10O2):
Q= nCpT
= 919.117 x 25.89 x 4
= 95183.76 kJ

Reactant (O2):
Q= nCpT
= 919.117 x 23.70 x 4
= 87132.29 kJ

Product (C14H8O2):
Q= nCpT
= (919.12 x 45.56 x 4)
= 167500.428 kJ

Product (H2O2):
Q= nCpT
= 919.117 x 67.34 x 4
= 247573.355 kJ
Product (H2O):
Q= nCpT
= 2.55 x 33.56 x4
= 342.312 kJ








HYDROGEN PEROXIDE
24

7.2 Energy Balance over Hydrogenation Unit

Quinone
167500.428
Amount of heat
added
-197095.718
Hydrogen
124779.05
Hydroquinone
95183.76
HYDROGE
NATOR

Energy Input in hydrogenation unit:

Quinone: 167500.428 kJ
Hydrogen: 124779.05 kJ

Energy out from hydrogenation unit:
Hydroquinone: 95183.76 kJ

Amount of heat added in hydrogenation unit: 197095.718 kJ

Table 7.2 Energy Balance over Hydrogenator


Material In Amount(kJ) Material Out Amount(kJ)
Quinone 167500.428 Hydroquinone 95183.76
Hydrogen 124779.05
Heat -197095.718
HYDROGEN PEROXIDE
25

7.3 Energy Balance over Oxidation Unit

OXIDATION UNIT
Working solution
182316.05
Hydroquinone
95183.76
Oxygen
87132.29

Energy Input in oxidation unit:

Hydroquinone: 95183.76 kJ
Oxygen: 87132.29 kJ

Energy out from hydrogenation unit:

Working solution: 182316.05 kJ


Amount of heat relies in hydrogenation unit: - 232415.421 kJ

Table 7.3 Energy Balance over Oxidation Unit



Material In Amount(kJ) Material Out Amount(kJ)
Hydroquinone 95183.76 Working solution 95183.76
Oxygen 87132.29
HYDROGEN PEROXIDE
26

7.4 Energy Balance over Extraction Unit


EXTRACTION UNIT
Quinone
167500.483
Working solution
182316.05
Hydrogen
peroxide
247573.355
Water
342.312

Energy Input in extraction unit:

Working solution: 182316.05 kJ
Water: 342.312 kJ

Energy out from hydrogenation unit:

Hydrogen peroxide: 247573.355 kJ
Quinone: 167500.483 kJ

Table 7.4 Energy Balance over Extractor

Material In Amount(kJ) Material Out Amount(kJ)
Working solution 182316.05 Hydrogen peroxide 247573.355
Water 342.312 Quinone 167500.483
HYDROGEN PEROXIDE
27

CHAPTER 8: PROCESS EQUIPMENT DESIGN

8.1 Hydrogenator Design
In the manufacturing of Hydrogen peroxide, hydrogenator is used. In this type of
reactor reactants are added to the vessel and the product is removed after completion
of process.
The design of reaction vessel contains the design of the shell, head, flanges, nozzles
and bolts.
The calculations are as follows:
Liquid flow rate =
24
82 . 191433

= 7976.40 kg/hour.
Gas flow rate=
24
23 . 1838

= 76.59 kg/hour.

8.1.1 Design of Shell
Capacity of the reactor is 8 tones and it is filled up to 2/3 height of the vessel. So the
volume of reactor is 9000 liter.
Data
Reactor volume (V) : 9000 liter
Diameter of shell (D
i
) : 1200 mm
Radius of shell(R) : 600 mm
Internal pressure : 0.101 N/ (mm)
2

Internal design pressure (p) : 0.101+0.03 = 0.131 N/ (mm)
2

Permissible design stress (f) : 130 N/ (mm)
2
(at 125 C)
Density of steel () : 7820 kg/ m
3


Calculation
Height of shell (H) =
2
R
V
[
=
( )
2
6 . 0 14 . 3
9000

= 7961.78 mm = 8000 mm


Thickness (ts) =
p J f
D p
i


2

HYDROGEN PEROXIDE
28

=
( ) 131 . 0 85 . 0 130 2
1200 131 . 0



= 0.71 mm
For rigidity minimum thickness of 4 mm is used. (no corrosion allowance.)

Weight of the vessel (W) = V
= ( ) | | [ H r r
2
1 2

= 7820 01608 . 0
=150kg
The stresses created due to combined loadings can be stated as:
1. Tensile stress in the circumferential direction due to internal pressure
f
t
=
( )
t
t D p
i

+
2

=
( )
4 2
4 1200 131 . 0

+

=19.71 N/ (mm)
2

2. Tensile Stress in the longitudinal direction due to internal pressure
f
1
=
t
D p
i

4

=
4 4
1200 131 . 0

=9.82 N/ (mm)
2


3. Compressive stress in longitudinal direction due to weight of vessel & contents.
f
2
=
( ) t D t
W
i
+ [

=
( )
1204 4
8 . 9 150 8000
[
+

=5.278 N/ (mm)
2


4. No wind load
f
3
=0
f
a
(tensile)=f
1
+f
2

HYDROGEN PEROXIDE
29

=9.82+5.278
=15.098 N/ (mm)
2


5. Stress due to offset piping wind
Torque due to offset piping= 500 N*mm.
f
s
=
( ) t D D t
T
i i
+ [
2

=
1204 1200 4
1000 500 2
[


=0.05 N/ (mm)
2


Tensile equivalent stress
f
R
= ( ) ( ) | |
5 . 0
2 2 2
3
s a a t t
f f f f f + +

= ( ) ( ) | |
5 . 0
2 2 2
05 . 0 3 098 . 15 098 . 15 72 . 19 72 . 19 + +
= 17.86 N/ (mm)
2

f
R
and f
a
both are less than the permissible tensile stress.

8.1.2 Design of Head

The internal design pressure is 0.131 N / mm2 and for this pressure torispherical
dished head can use.
Torispherical head have the dish or crown radius equal to or less than the diameter of
the head. To reduce the stress at corner of the head, a knuckle is formed with a radius
of at least 6% of inside diameter.

Data
Radius of head= 1200 mm
Crown radius (R
c
) =1200 mm
Stress identification factor (W) =
|
|
.
|

\
|
+
1
3
4
1
R
R
c

=
|
|
.
|

\
|
+
72
1200
3
4
1

HYDROGEN PEROXIDE
30

= 1.77
Thickness of head
J f
W R p
t
C
h


=
2


1 130 2
77 . 1 1200 131 . 0


=
= 1.07 mm
Use 4mm thickness of head (no corrosion allowance)

8.1.3 Design of Half Coil Jacket

Data
Diameter of half coil (d
1
) = 100 mm
Design pressure (P) = 0.35 N/ mm
2

Allowable stress (f
c
) = 98 N/ mm
2


Calculation
Thickness of half coil
c
C
f
d P
t

=
2
1


98 2
100 35 . 0

=
=0.17 mm
So use 3 mm thick plate.
Circumferential stress in the shell
F
ps
=
( )
|
|
.
|

\
|
+

+
|
|
.
|

\
|

s c
i
s
i
t t
D P
t
D P
5 . 2 4 2



( ) ( )
|
|
.
|

\
|
+

+
|
.
|

\
|

=
4 5 . 2 3 4
100 35 . 0
4 2
1200 101 . 0

=16.7 N/mm
2


Longitudinal stress in the shell at the junction of the coil
HYDROGEN PEROXIDE
31

|
|
.
|

\
|

A
+
|
|
.
|

\
|

+
|
|
.
|

\
|

=
2
2
3
2
4 4
s
o
s
i
s
i
as
t
d P
t
D P
t
D P
f

( )
( )
|
|
.
|

\
|

+
|
.
|

\
|

+
|
.
|

\
|

=
2
2
4 2
104 249 . 0 2
3 2
100 35 . 0
4 4
1200 131 . 0

=63.65 N/mm
2
This is less than the allowable stress value of 98 N/mm
2
.

8.1.4 Design of Nozzle Reinforcement

Data
Internal diameter= 150 mm
Internal design pressure= 0.131 N/mm
2

Calculation
Minimum nozzle thickness
( ) P J f
D P
t
i
n


=
2


( ) 131 . 0 1 130 2
150 131 . 0


=
Maximum horizontal distance for compensation
150 2 =
= 300 mm

Maximum vertical distance for compensation
66 . 2 6 =
=15.96 mm

Area of compensation
66 . 2 150 =
= 400 mm
2

Area of compensation provided by head
( ) '
s s s
t t d A = , where t
s
=original thickness
HYDROGEN PEROXIDE
32

t
s
=theoretical thickness

( ) 71 . 0 4 150 =
s
A

=493.5 mm
2


Area of compensation provided by nozzle
( ) ' 2
1 0 n n
t t H A =
( ) 07 . 0 3 3 5 . 2 2 =
= 44 mm
2

The nozzle does not project inside vessel, H
2
=0
A
1
= 0
Total area compensation = 537.5 mm
2

This is satisfactory, therefore no additional compensation required.

8.1.5 Design of Agitator
It is more preferred to buy Philadelphia agitator, which give lower power
consumption and better mixing.
Type of agitator = turbine agitator
Straight blade type having insulation for protecting against corrosion
Diameter of agitator = 1/3 x 1200
= 400 mm
Maximum speed = 120 rpm
Internal pressure = 0.88 N/mm
2

Liquid in vessel specific gravity = 1.161
Viscosity, = 600 cp- more excess than process liquid
Thickness of blade = 1/5 x 400
= 80 mm
No of blade = 4
Shaft material = Cold rolled steel
Permissible stress in a shaft = 55 N/mm
2

Elastic limit in tension = 246 N/mm
2

Modulus of Elasticity = 19.5 x 10
4
N/mm
2

Permissible stress for key
MOC = CS
HYDROGEN PEROXIDE
33

Shear = 65 N/mm
2

Crushing = - 30 N/mm
2

Stuffing box = CS
Permissible stress = 58.7 N/mm
2

Baffle width = Di/12
= 1200/12
= 100 mm
Baffle Height = 2.5 x 400
= 1000 mm
Offset = 1/5 width
= 20 mm

Location of Agitator:-
- Height from bottom > Diameter of Agitator, Da
- Total liquid Height = 5.3 m
- Total tank height = 8 m
- Submerging of agitator = 4 to 6
- Taking submerging = 5 x 400 = 2000 mm
- Height from bottom = 1250 mm
- Total shaft overhang = Total height -1250 + 20 above vessel
= 6770 mm
- Power required of agitator,
Nre = N Da
2
/
= 1.161 x 1000 x 120 x 400
2
x 1000/(60 x 600 x 10
6
)
= 619.23
from power curve,
Np = 3.8

P = Np x x N
3
x Da
5
/(gc x 75)
= 2.16 Hp

Gland loss = 10% of P
= 0.216 Hp
HYDROGEN PEROXIDE
34

Transmission loss = 20 %
= 0.432 Hp

Total Hp = 2.808 Hp
Take 3 Hp considering fitting losses and done calculation.

Shaft design:-
Continuous average rated torque on shaft
T = Hp x 750 x 60/ (2N)
= 3 x 750 x 60/ (2 x 120)
= 179.140 Nm

Tmax = 1.5 T
= 268.710 Nm
Now fs = Tmax/ Zp
Where,
fs = Permissible shear stress
Zp = Polar Modulus of shaft section

- Zp = Tmax/ fs
= 268.710 x 1000/55
= 48.85 cm3

- d
3
= 16 x Zp/
= 16 x 48.85/
d = 29.19 cm

Now torque Tmax is resisted by a force Fm acting at a radius of 0.75 R
b
from the axis
of the agitator shaft.
Fm = Tmax/ (0.75 R
b
)
Where,
Rb = radius of blade
Fm = 268.710/ (0.75 x 0.2)
HYDROGEN PEROXIDE
35

=1791.4 N
The maximum bending moment occurs at a point near bearing,
M = Fm x l
Where,
L = shaft overhang
M = 1791.4 x 6.67
= 11948.638 Nm

The equivalent bending moment is given by,
Me = [M + (M + Tmax)
1/2

= [11948.638 + (11948.638 + 268.710)
1/2
]
= 6029.58 Nm

The stress due equivalent bending moment,
f = Me/Z
where,
Z = Modulus of section
= d
3
/32
f = 6029.58 x 32 x 1000/ ( x 400
3
)
= 960.12 N/mm
2

Here f> 246 N/mm
2

Use 8 cm diameter shaft
We get f = 120.01 N/mm
2

Now deflection of shaft,
= WL
3
/ (3 x E x I)
Where,
W = concentrated load
L = Appropriate length
I = moment of inertia = x d
4
/64
= 3222.82 x 6770
3
x 64/ (3 x 19.5 x 10
6
x x 8
4
)
= 4.506 cm
The critical speed is calculated as
Nc = 60 x 4.987/ (4.506)
1/2

= 140.95 rpm
HYDROGEN PEROXIDE
36

which is 85.13 % of max. speed

8.2 Design of Storage Tank

Production of hydrogen peroxide is 31250 kg/day.

Volume of the storage tank: 350 m
3

8.2.1 Volume of shell

V = D
2
H
4
We have D: H = 8:3
So, D = 8 H
3
V = x 8 H
2
H
4 3

350 = x 64 x H
3

4 9
H=3.97
~ 4 m
D = 10.59 m.
11 m

8.2.2 Thickness of shell:
t
s
= PD + CA
2fJ
Where, P = (H 0.3) x
fluid
x g / g
c

= (4 0.3) x 1450 x 10
= 53650 N/ m
2

=0.053650 N/ mm
2
f (allowable stress) = 142 N / mm
2
HYDROGEN PEROXIDE
37


C.A. (corrosion allowance) = 0 mm

J (joint efficiency) = 0.85

So, ts = 0.053650 x 11,000
2 x142 x 0.85
= 2.44 mm
5 mm

Minimum shell thickness is 5 mm.
So, ts = 5 mm.

8.2.3 Calculation for No. of plates:

No. of horizontal plates = n
H
= d
L + 2x10
-3

= x 11
6 + 2x10
-3

= 5.75
6
No. of vertical plates = n
v
= H + 2x10
-3

W + 2x10
-3
= 4 + 2x10
-3
1.5 + 2x10
-3
= 3.103
5 plates
Total no. of plates = n
s
= n
H
x nv
= 6 x 5
= 30 plates
8.2.4 Bottom design

Base dia. D
b
= D
s
+ 2 ts + 2 x welding thickness + (2 x 0.00254)
= 11 + (2 x0.005) +(2 x0.002) + (0.050)
HYDROGEN PEROXIDE
38

= 11.01908 m
No. of Base plates = N = ( / 4) D
b
2
L x W
= ( / 4) x (11.01908)
2

6 x 1.5
= 10.5905
= 12.0 plates

8.2.5 Conical roof design

Assuming that self-supporting type conical roof can be used.
Thickness of salt supporting roof:
Take tr = 20 mm
Pr = dead load + live load
= 1250 + (tr x
moc
x g/gc)
= 1250 + (0.020 x 7750 x 10)
= 2800 N / mm
2

= 2.8 x 10
-3


Sin = Pr D
0.204 x E tr


Sin = [0.00125+(20 x 7750 x 10
-9
x 10)]
1/2
x 11019/20
0.204 x 1.9 x 10
5




Sin = 0.147
Tan = 0.1532 <0.2

Assume tr= 14 mm
Sin = 0.194
Tan = 0.1967< 0.2
HYDROGEN PEROXIDE
39

So, Design is Safe for tr= 14 mm.


A
1
= P* D
2
* Cot
8*f
=[0.00125+(14*7750*10
-9
*10)]*(11*10
3
)
2
*{1/0.1967}
8 *142

A
1
= 587.52 mm
2

A
2
= A
c
+A
s
+A
r

A
c
= 65*65
= 4225 mm
2

A
s
= 1.5 t
r
*(R* t
r
)
1/2
R=D/2=11019/2=5509.5
= 1.5 * 5*(5509.5*5)
1/2
=1244.80 mm
2

A
r
= 0.75* t
r
* (r * t
r
)
1/2

r= D/2
Sin
= 5509.5
0.194
=28399.48

A
r
= 0.75* 5*(28399.5 * 5)
1/2
= 1413.09 mm
2


A
2
= 4225 + 1244.80 + 1413.09
= 6882.89 mm
2


A
2
> A
1
So, Design is safe.

HYDROGEN PEROXIDE
40

CHAPTER 9: PROCESS CONTROL


Effective process control can be accomplished with responsive control loops for flow,
pressure, temperature, and level. Plants built in recent years and retrofits in older
plants have applied instruments for detecting liquid-phase interfaces as well as for
composition analysis at various points. The most recently built plants utilize state-of -
art electronic instrumentation. The characteristics of the extractor require particularly
stable operation with respect to flow rate and composition changes.

The largest proportion of heat exchanger in the process is for cooling since both
hydrogenation and oxidation are exothermic. At steady state, small heat inputs are
used to establish the desired temperatures in working solution regeneration, water
control, and solvent adsorption on the oxidizer exit gas if this auxiliary is used.

Periodic heat inputs are needed to desorb adsorbent beds.

Provision is necessary to keep the working solution inventory above its precipitation
temperature when heats of reaction are not present during shutdowns.

9.1 Pressure Measurement

Pressure is defined as the force exerted over a unit area. Force may be exerted by
liquid, gases and solids. Mathematically, pressure is expressed as:

P = F/A

where,
p is pressure, f is force, A is area.
Pressure is normally expressed in pounds per square inch (psi).



HYDROGEN PEROXIDE
41

9.1.1 Pressure Gauge

The bourdon tube is most frequently used in the pressure gauge. A bourdon tube
consist of a long think walled cylinder of non circular cross section sealed at the end,
made from materials such as phosphor bronze, steel & beryllium copper, and attached
by a light line work to the mechanism which operates the pointer. The other and of
tube is fixed and is open for the application of the pressure which is to be measured.

The tube is soldered or wended to a socket at the based, through which pressure
connection is made. Bourdon tube is available in many shapes like, c type, spiral, &
helical.

Advantages:9.1.1 Pressure Gauge

1. Cost is low
2. Construction is simple
3. Life is long
4. Efficiency is high
5. Tubes are in different range

Disadvantages:

1. Spring gradient is low (50psig)
2. Shock and vibration effect.


9.2 Temperature Measurement

Temperature has been defined in a variety of ways. One example defines temperature
as the measure of heat associated with the movement of the molecules of a substance.
This definition is based on the fact that the molecules of all matter are in continuous
motion that is sensed as heat.


HYDROGEN PEROXIDE
42

Another definition is based on the concept of thermodynamics. Thermal energy
always flows from a warmer body to a cooler body. In this case, temperature is
defined as an intrinsic property of matter that quantifies the ability of the one body to
transfer thermal energy to another body. If two bodies are in thermal equilibrium and
no energy is exchanged, the bodies are at the same temperature.

In simplest terms, the temperature is the measurement of the hotness or coldness of
the body.

- Temperature Measuring Devices

(1) Thermocouple

(2) RTD


9.3 Flow Measurement

Flow is one of the most difficult process variables to measure accurately. One of the
simplest methods for determining the flow rate is the fluid per unit time method,
which

assumes a basic premise of the fluid mechanics that mass is a conserved quantity. The
mass entering a system is equal to the mass leaving the system and both are measured
over the same time interval.

This method for accurate flow measurement takes into consideration two basic
properties of fluid, which are density and viscosity and their effect on the accuracy of
flow measurement.




HYDROGEN PEROXIDE
43

- Density:

Density is a measurement of the proximity of the molecules that make up a
substance. In the simplest terms, density is mass per unit volume. This can be
expressed as:
= m/V

where,
is density, m mass and V is volume.

It is density that causes the same volume of different substance to differ in weight. It
is typically expressed in pounds/cubic foot.

- Viscosity:

It is property of the measure how freely the fluid flows. The unit of the viscosity is
centipoises.

- Specific gravity:

It is the ratio of the density of the fluids at a specific temperature to the density of the
water or air at the same temperature. The specific gravity is a dimensionless quantity.

- Reynolds number:

The Reynolds number is the ratio of the internal to viscous forces to flow condition.
R = internal forces/viscous forces = VD /

- Differential Pressure Meter

The basic equation from the Bernoullis theorem is,
Q = CA2gh

HYDROGEN PEROXIDE
44

Where,
Q is flow,
C is orifice coefficient,
A cross sectional area of the restriction,

g is gravitational constant
h is differential pressure.

- Orifice Plates

Orifice plates are the simplest and cheapest form of primary flow measuring elements
and are used more frequently then all other types. An orifice plate is inserted in the
pipeline perpendicular the flow and differential pressure across it is measured. There
are four types of orifice plates, which are concentric, eccentric, segmental, quadrant
edge.

9.4 Level Measurement

Level is measured at the position of the interface between phases, where the phases
are liquid/gas, solid/gas, or immiscible liquid/liquid. Level is simply a measure of
height defining the position of the interface that is the surface where the two phases
meet with respect to a reference point. This measurement is often converted to a
volumetric or gravimetric quantity. So level may be measured directly by defining the
position of the interface or indirectly by measuring another quantity, such as volume
and interfacing the level measurement by converting the quantity to a level
measurement.

Level is a vertical measurement taken from the surface or interface to a fixed point.
Normally the reference point is the bottom of the vessel holding the substance. As
with most process variables, level can be measured by both direct and indirect
methods.


HYDROGEN PEROXIDE
45

- Level gauge
- Displacer level detector
- Ultrasonic level detector
- Differential pressure level detector

9.5 pH METER

Method have been developed which minimizes the problems encountered when
measuring Ph in pure waters. The method uses a quality glass pH electrode and
special set of a pure water pH additive & a special solution of diluted buffers
containing the same background of pure water pH additive.

Adding the pure water pH additive to the samples increases the ionic strength thus
reducing the noise and improving time. The shift in pH caused by the addition of the
pure water pH additive is minimal, between 0.005 & 0.01 pH units, since the same

amount of pure water pH additive is added to the buffers and samples the net effect on
the pH is negligible.

















HYDROGEN PEROXIDE
46

CHAPTER 10: MATERIAL SAFETY DATA SHEET

Hydrogen Peroxide

1. Product And Company Identification

Product Name: Hydrogen Peroxide (20 to 40%)

Alternate Product Name(S): Durox Reg. & LR 35%, Oxypure 35%, Standard
27.5 & 35%,
Super D 25 & 35, Technical 35%, HTP 35%, OHP 35%, Chlorate Grade, 20%,
Semiconductor Reg, Seg, RGS, RGS 2, RGS 3, 31%

General Use:
Durox 35% Reg. & LR - meets the Food Chemical Codex requirements for aseptic
packaging and other food related applications.
Oxypure 35% - certified by NSF to meet NSF/ANSI Standard 60 requirements for
drinking water treatment.
Standard 27.5 and 35% - most suitable grade for industrial bleaching, processing,
pollution abatement and general oxidation reactions.
Semiconductor Reg, Seg, RGS, RGS 2, RGS 3, 31% - conform to ACS and Semi
Specs. for wafer etching and cleaning, and applications requiring low residues.
Super D 25 and 35% - meets US Pharmacopoeia specifications for 3% topical
solutions when diluted with proper quality water. While manufactured to the USP
standards for purity and to FMC's demanding ISO 9002 quality standards, FMC does
not claim that it's Hydrogen Peroxide is manufactured in accordance with all
pharmaceutical cGMP conditions.
Technical 35% - essentially free of inorganic metals suitable for chemical synthesis.
HTP 35% - specially formulated for aerospace equipment conditioning.
OHP 35% - specially formulated for OHP process, advanced oxidation, and activated
peroxide applications
Chlorate Grade 20% - specially formulated for use in chlorate manufacture or
processing.
HYDROGEN PEROXIDE
47

Hydrogen Peroxide (20 to 40%) (7722-84-1-3) Date: 06/03/2008

Manufacturer

FMC CORPORATION
FMC Peroxygens
1735 Market Street
Philadelphia, PA 19103
(215) 299-6000 (General Information)
msdsinfo@fmc.com (Email - General Information)
FMC of Canada Ltd.
FMC Peroxygens
PG Pulp Mill Road
Prince George, BC V2N2S6
(250) 561-4200 (General Information)

Emergency Telephone Numbers

(281) 474-8750 (Plant: Pasadena, TX, US - Call Collect)
(250) 561-4221 (Plant: Prince George, BC, Canada - Call
Collect)
(303) 595-9048 (Medical - U.S. - Call Collect)
For leak, fire, spill, or accident emergencies, call:
(800) 424-9300 (CHEMTREC - U.S.A.)
(613) 996-6666 (CANUTEC - Canada)

2. Hazards Identification

Emergency Overview
Clear, colorless, odorless liquid
Oxidizer.
Contact with combustibles may cause fire.
Decomposes yielding oxygen that supports combustion of organic matters and can
cause overpressure if confined.
HYDROGEN PEROXIDE
48

Corrosive to eyes, nose, throat, lungs and gastrointestinal tract.

Potential Health Effects: Corrosive to eyes, nose, throat and lungs. May cause
irreversible tissue damage to the eyes including blindness. May cause skin irritation.

3. Composition / Information On Ingredients
Hydrogen Peroxide 7722-84-1 20 - 40 231-765-0 O, C, Xn; R5- R8-R35- R20/22
Water 7732-18-5 60 - 80 231-791-2 Not classified
Hydrogen Peroxide (20 to 40%) (7722-84-1-3) Date: 06/03/2008

4. First Aid Measures

Eyes: Immediately flush with water for at least 15 minutes, lifting the upper and
lower eyelids intermittently. See a medical doctor or ophthalmologist immediately.
Skin: Wash with plenty of soap and water. Get medical attention if irritation occurs
and persists.
Ingestion: Rinse mouth with water. Dilute by giving 1 or 2 glasses of water. Do not
induce vomiting. Never give anything by mouth to an unconscious person. See a
medical doctor immediately.
Inhalation: Remove to fresh air. If breathing difficulty or discomfort occurs and
persists, contact a medical doctor.
Notes to Medical Doctor: Hydrogen peroxide at these concentrations is a strong
oxidant. Direct contact with the eye is likely to cause corneal damage especially if not
washed immediately.
Careful ophthalmologic evaluation is recommended and the possibility of local
corticosteroid therapy should be considered. Because of the likelihood of corrosive
effects on the gastrointestinal tract after ingestion, and the unlikelihood of systemic
effects, attempts at evacuating the stomach via emesis induction or gastric lavage
should be avoided.

5. Fire Fighting Measures

Extinguishing Media: Flood with water.
Fire / Explosion Hazards: Product is non-combustible. On decomposition releases
HYDROGEN PEROXIDE
49

oxygen which may intensify fire.
Fire Fighting Procedures: Any tank or container surrounded by fire should be
flooded with water for cooling. Wear full protective clothing and self-contained
breathing apparatus.
Flammable Limits: Non-combustible
Sensitivity To Impact: No data available
Sensitivity To Static Discharge: No data available


6. Accidental Release Measures

Release Notes: Dilute with a large volume of water and hold in a pond or diked area
untilhydrogen peroxide decomposes. Hydrogen peroxide may be decomposed by
adding sodium metabisulfite or sodium sulfite after diluting to about 5%. Dispose
according to methods outlined for waste disposal.
Hydrogen Peroxide (20 to 40%) (7722-84-1-3) Date: 06/03/2008
Combustible materials exposed to hydrogen peroxide should be immediately
submerged in or rinsed with large amounts of water to ensure that all hydrogen
peroxide is removed. Residual hydrogen peroxide that is allowed to dry (upon
evaporation hydrogen peroxide can concentrate) on organic materials such as paper,
fabrics, cotton, leather, wood or other combustibles can cause the material to ignite
and result in a fire.

7. Handling And Storage

Handling: Wear chemical splash-type monogoggles and full-face shield, impervious
clothing, such as rubber, PVC, etc., and rubber or neoprene gloves and shoes. Avoid
cotton, wool and leather. Avoid excessive heat and contamination. Contamination
may cause decomposition and generation of oxygen gas which could result in high
pressures and possible container rupture. Hydrogen peroxide should be stored only in
vented containers and transferred only in a prescribed manner (see FMC Technical
Bulletins).
HYDROGEN PEROXIDE
50

Never return unused hydrogen peroxide to original container, empty drums should be
triple rinsed with water before discarding. Utensils used for handling hydrogen
peroxide should only be made of glass, stainless steel, aluminum or plastic.

Storage: Store drums in cool areas out of direct sunlight and away from
combustibles. For bulk storage refer to FMC Technical Bulletins.

Comments: VENTILATION: Provide mechanical general and/or local exhaust
ventilation to prevent release of vapor or mist into the work environment.

8. Exposure Controls / Personal Protection

Exposure Limits
Hydrogen Peroxide 1 ppm (TWA) 1 ppm (PEL) 1.4 mg/m3 (PEL)
Engineering Controls: Ventilation should be provided to minimize the release of
hydrogen peroxide vapors and mists into the work environment. Spills should be
minimized or confined immediately to prevent release into the work area. Remove
contaminated clothing immediately and wash before reuse.

Personal Protective Equipment

Eyes And Face: Use chemical splash-type monogoggles and a full-face shield made
of polycarbonate, acetate, polycarbonate/acetate, PETG or thermoplastic.

Respiratory: If concentrations in excess of 10 ppm are expected, use NIOSH/DHHS
approved self-contained breathing apparatus (SCBA), or other approved atmospheric-
supplied respirator (ASR) equipment (e.g., a full-face airline respirator (ALR)). DO
NOT use any form of air-purifying respirator (APR) or filtering facepiece (AKA dust
mask), especially those containing oxidizable sorbants such as activated carbon.
Hydrogen Peroxide (20 to 40%) (7722-84-1-3) Date: 06/03/2008

Protective Clothing: For body protection wear impervious clothing such as an
approved splash protective suit made of SBR Rubber, PVC (PVC Outershell
w/Polyester Substrate), Gore-Tex (Polyester trilaminate w/Gore-Tex), or a specialized
HYDROGEN PEROXIDE
51

HAZMAT Splash or Protective Suite (Level A, B, or C). For foot protection, wear
approved boots made of NBR, PVC, Polyurethane, or neoprene. Overboots made of
Latex or PVC, as well as firefighter boots or specialized HAZMAT boots are also
permitted. DO NOT wear any form of boot or overboots made of nylon or nylon
blends. DO NOT use cotton, wool or leather, as these materials react RAPIDLY with
higher concentrations of hydrogen peroxide. Completely submerge hydrogen peroxide
contaminated clothing or other materials in water prior to drying. Residual hydrogen
peroxide, if allowed to dry on materials such as paper, fabrics, cotton, leather, wood
or other combustibles can cause the material to ignite and result in a fire.

Gloves: For hand protection, wear approved gloves made of nitrile, PVC, or
neoprene. DO NOT use cotton, wool or leather for these materials react RAPIDLY
with higher concentrations of hydrogen peroxide. Thoroughly rinse the outside of
gloves with water prior to removal. Inspect regularly for leaks.


9. Physical And Chemical Properties

Odor: Odorless
Appearance: Clear, colorless liquid
Auto-ignition Temperature: Non-combustible
Boiling Point: 103C/218F (20%); 107C/225F (31%); 108C/226F(35%)
Coefficient Of Oil / Water: Not available
Density / Weight Per Volume: Not available
Evaporation Rate: > 1 (Butyl Acetate = 1)
Flash Point: Non-combustible
Freezing Point: -15C/6F (20%); -26C/-15F (31%); -33C/-27F (35%)
Odor Threshold: Not available
Oxidizing Properties: Strong oxidizer
Percent Volatile: 100
pH: <= 3.7, 5.0 - 6.0 @ 25 C (1% solution)
Solubility In Water: 100 %
Specific Gravity: 1.07 @ 20C/4C (20%); 1.11 @ 20C/4C (31%); 1.13 @20C/4C
(35%)
HYDROGEN PEROXIDE
52

Vapor Density: (Air = 1): Not available
Vapor Pressure: 28 mmHg @ 30C (20%); 24 mmHg @ 30C (31%); 23 mmHg @
30C (35%)
Hydrogen Peroxide (20 to 40%) (7722-84-1-3) Date: 06/03/2008

10. Stability And Reactivity

Conditions To Avoid: Excessive heat or contamination could cause product to
become unstable.
Stability: Stable (heat and contamination could cause decomposition)
Polymerization: Will not occur
Incompatible Materials: Reducing agents, wood, paper and other combustibles, iron
and other heavy metals, copper alloys and caustic.
Hazardous Decomposition Products: Oxygen which supports combustion.
Comments: Materials to Avoid: Dirt, organics, cyanides and combustibles such as
wood, paper, oils, etc.

11. Toxicological Information

Eye Effects: 35% hydrogen peroxide: Extremely irritating/corrosive (rabbit) [FMC
Study
Number: I83-748]
Skin Effects: 35% hydrogen peroxide: Mildly irritating after 4-hour exposure (rabbit)
[FMC Study Number: I83-747]
Dermal Ld50: 35% Hydrogen Peroxide: > 2,000 Mg/Kg (Rabbit) [Fmc Study
Number: I83-746]
Oral Ld50: 35% hydrogen peroxide: 1,193 mg/kg (rat) [FMC Study Number: I83-
745]
Inhalation LC50: 50% hydrogen peroxide: > 0.17 mg/l (rat) [FMC Study Number:
I89-1080]
Target Organs: Eyes, nose, throat and lungs
Acute Effects From Over exposure: Extremely irritating/corrosive to eyes and
gastrointestinal tract. May cause irreversible tissue damage to the eyes including
HYDROGEN PEROXIDE
53

blindness. Inhalation of mist or vapors may be severely irritating to nose, throat and
lungs. May cause skin irritation.
Chronic Effects From Over exposure: The International Agency for Research on
Cancer (IARC) has concluded that there is inadequate evidence for carcinogenicity of
hydrogen peroxide in humans, but limited evidence in experimental animals (Group 3
- not classifiable as to its carcinogenicity to humans). The American Conference of
Governmental Industrial Hygienists (ACGIH) has concluded that hydrogen peroxide
is a Confirmed Animal Carcinogen with Unknown Relevance to Humans (A3).
Hydrogen Peroxide (20 to 40%) (7722-84-1-3) Date: 06/03/2008


Carcinogenicity:
Chemical Name IARC NTP OSHA Other
Hydrogen Peroxide Not listed Not listed Not listed (ACGIH) Listed (A3, Animal
Carcinogen)

12. Ecological Information

Ecotoxicological Information: Channel catfish 96-hour LC50 = 37.4 mg/L
Fathead minnow 96-hour LC50 = 16.4 mg/L
Daphnia magna 24-hour EC50 = 7.7 mg/L
Daphnia pulex 48-hour LC50 = 2.4 mg/L
Freshwater snail 96-hour LC50 = 17.7 mg/L
For more information refer to ECETOC "Joint Assessment of Commodity Chemicals
No. 22, Hydrogen Peroxide." ISSN-0773-6339, January 1993

Chemical Fate Information: Hydrogen peroxide in the aquatic environment is
subject to various reduction or oxidation processes and decomposes into water and
oxygen. Hydrogen peroxide half-life in freshwater ranged from 8 hours to 20 days, in
air from 10-20 hrs. and in soils from minutes to hours depending upon
microbiological activity and metal contaminants.



HYDROGEN PEROXIDE
54

13. Disposal Considerations

Disposal Method: An acceptable method of disposal is to dilute with a large amount
of
water and allow the hydrogen peroxide to decompose followed by discharge into a
suitable treatment system in accordance with all regulatory agencies. The appropriate
regulatory agencies should be contacted prior to disposal.







































HYDROGEN PEROXIDE
55

CHAPTER 11: SAFETY AND HANDLING

11.1 Environmental Applications
Stand-Alone Applications
Odor control - Oxidizes hydrogen sulfide, mercaptans, amines and aldehydes.
H2O2 may be applied directly to aqueous wastes containing these odorants, or to
wet scrubbers used to remove them from airstreams. If the odors are the result of
biological activity, H2O2 may instead be added as a preventative to eliminate the
anoxic conditions which favor the generation of odors.
Corrosion control - destroys residual chlorine and reduced sulfur compounds
thiosulfates, sulfites, and sulfides) which form corrosive acids when condensed
onto processing equipment and oxidized by air.
BOD/COD removal - Oxidizes both organic and inorganic pollutants which
contribute to BOD and COD -- catalytic, H2O2 may be needed to oxidize the
more resistant substances. H2O2 may also affect BOD/COD removal by
enhancing the performance of other processes.
Inorganic oxidation - Oxidizes cyanides, NOx/SOx, nitrites, hydrazine, carbonyl
sulfide, and other reduced sulfur compounds mentioned above (odor/corrosion
control).
Organic oxidation - Hydrolyzes formaldehyde, carbon disulfide, carbohydrates,
organophosphorus and nitrogen compounds, and various water-soluble polymers;
and (with catalysis) destroys phenols, BTEX pesticides, solvents, plasticizers,
chelants, and virtually any other organic requiring treatment.
Metals oxidation - Oxidizes ferrous iron, manganese, arsenic, and selenium to
improve their adsorption, filtration, or precipitation from process waters and
wastewaters.
HYDROGEN PEROXIDE
56

Toxicity reduction/Biodegradability improvement - With catalysis, chemically
digests complex organics into smaller, less toxic and more biodegradable
fragments.
Hydrogen peroxide is well-established as an environmentally-friendly deodorizing
and bleaching agent. Its uses include organic and inorganic chemical processing,
textile and pulp bleaching, metal treating, cosmetic applications, catalysis of
polymerization reactions, municipal odor control, industrial waste treatment
(detoxification), and control of bulking in wastewaters. These uses are continually
expanding, making it a necessity not only to understand the mode of hydrogen
peroxide application but the safe handling of the chemical as well.
11.2 Hazards
Hydrogen peroxide, either in pure or diluted form, can pose several risks:
Above roughly 70% concentrations, hydrogen peroxide can give off vapor that can
detonate above 70 C (158 F) at normal atmospheric pressure. This can then cause a
boiling liquid expanding vapor explosion of the remaining liquid. Distillation of
hydrogen peroxide at normal pressures is thus highly dangerous.
Hydrogen peroxide vapors can form sensitive contact explosives with hydrocarbons
such as greases. Hazardous reactions ranging from ignition to explosion have been
reported with alcohols, ketones, carboxylic acids (particularly acetic acid), amines and
phosphorus. The saying is 'peroxides kill chemists. Hydrogen peroxide, if spilled on
clothing (or other flammable materials), will preferentially evaporate water until the
concentration reaches sufficient strength, then clothing will spontaneously ignite.
Leather generally contains metal ions from the tanning process and will often catch
fire almost immediately.
Concentrated hydrogen peroxide (>50%) is corrosive, and even domestic-strength
solutions can cause irritation to the eyes, mucous membranes and skin. Swallowing
hydrogen peroxide solutions is particularly dangerous, as decomposition in the
stomach releases large quantities of gas (10 times the volume of a 3% solution)
leading to internal bleeding. Inhaling over 10% can cause severe pulmonary irritation.
Low concentrations of hydrogen peroxide, on the order of 3% or less, will chemically
HYDROGEN PEROXIDE
57

stain any clothing it comes into contact with a pinkish hue. Caution should be
exercised when using common products that may contain hydrogen peroxide, such as
facial cleaner or contact lens solution, which easily splatter upon other surfaces.
Hydrogen peroxide is naturally produced as a byproduct of oxygen metabolism, and
virtually all organisms possess enzymes known as peroxides, which apparently
harmlessly catalytically decomposes low concentrations of hydrogen peroxide to
water and oxygen.
Hydrogen peroxide was also part of the ingredients in the July 21, 2005 London
Underground bombs, which failed to explode.
11.3 Properties of Hydrogen Peroxide
A basic understanding of the properties of hydrogen peroxide is essential to the safe
handling of this chemical. Hydrogen peroxide is clear, colorless, waterlike in
appearance, and has a characteristic pungent odor. Nonflammable, it is miscible with
water in all proportions and is sold as a water solution.
The amount of hydrogen peroxide in commercial solutions is expressed as a
percentage of the solution's weight. Thus, a 35% solution contains 35% hydrogen
peroxide and 65% water by weight. Most municipal and industrial applications call
for 35% or 50% concentrations.

11.4 Delivery and Storage
The methods available for delivery to bulk storage installations accommodate
shipments of 70% hydrogen peroxide for dilution to the 35% or 50% storage
concentrations. Solutions containing more than 8% hydrogen peroxide are classified
by the U.S. Department of Transportation (DOT) as an oxidizer.
Under normal conditions hydrogen peroxide is extremely stable when properly stored.
Rate loss in large containers such as tanks is less than 1% per year at normal ambient
temperatures; in small containers, such as drums, rate loss is less than 2% per year.
HYDROGEN PEROXIDE
58

The larger the ratio of the storage container surface areas to the volume of hydrogen
peroxide, the greater the rate loss.
Decomposition of hydrogen peroxide liberates oxygen and heat. In dilute solutions the
heat evolved is readily absorbed by the water present. In more concentrated solutions,
the heat raises the temperature of the solution and accelerates the decomposition rate.
Special stabilizers are added during the manufacture of all grades of hydrogen
peroxide to inhibit the catalytic decomposition effect of metals and other impurities
that may accidentally contaminate the chemical during shipment, storage, and
handling.
However, since no additive will prevent decomposition if excessive contamination
occurs, the best practice is to prevent contamination through proper handling. All
handling procedures must, therefore, be directed towards maintaining the same degree
of purity and freedom from contamination as is maintained during the manufacturing
process:
- Storage of hydrogen peroxide should be restricted to its original shipping
container or to properly designed containers made of compatible materials
which have been thoroughly passivated.
- Hydrogen peroxide that has been removed from the original shipping
container should not be returned to it.
- All containers must be properly vented, and preferably stored away from
sources of direct heat and combustible materials.
- Adequate ventilation and ample water supply for thorough flushing of
accidental spillage on personnel and property should be provided.

Hydrogen peroxide itself will not burn, but its decomposition liberates oxygen which
supports combustion. Fires involving hydrogen peroxide are best controlled by using
large quantities of water.
HYDROGEN PEROXIDE
59

Hydrogen peroxide is not considered an explosive. However, when it is mixed with
organic substances at significant concentrations, hazardous impact-sensitive
compounds may result. Small amounts of other materials that contain catalysts (silver,
lead, copper, chromium, mercury, and iron oxide rust) can cause rapid decomposition
and an explosive pressure rupture of the containing vessel if it is not properly vented.
In addition to accelerated decomposition through contamination, the decomposition
rate of hydrogen peroxide is increased with alkalinity, contact with certain materials
of construction, and increasing temperatures. The rate of decomposition increases
approximately 2.2 times for each 10 degrees C rise in temperature in the range from
20 degrees C to 100 degrees C, or 1.5 times for each 10 degrees F rise from 68
degrees F to 212 degrees F.
Decreasing temperatures have little effect on hydrogen peroxide until they drop
substantially below 0 degrees C. Crystals do not begin to appear in 35% and 50%
solutions until -33C (-27.4F) and -52.2C (-62F), respectively.

11.5 Eye Protection
Hydrogen peroxide and its decomposition products are not systematic poisons but
contact with hydrogen peroxide can be irritating. Concentrated vapors cause
discomfort in the mucous membranes and the eyes. Contact of the eyes with hydrogen
peroxide is particularly dangerous because corneal burns can occur very rapidly.
Therefore, safety glasses or, preferably, goggles should always be worn when
handling concentrated hydrogen peroxide. If, however, any hydrogen peroxide does
get in the eyes, flush eyes thoroughly with water and consult a physician promptly.

11.6 Protective Clothing
In addition to eye protection, rubber gloves and suitable protective clothing such as
aprons or coveralls made of polyester acrylic fiber, polyvinyl chloride, polyethylene,
or neoprene should be worn when handling concentrated hydrogen peroxide.
Protective clothing, which lacks fire resistance, must be washed thoroughly with
HYDROGEN PEROXIDE
60

water should it come in contact with hydrogen peroxide. If allowed to dry in the
fabric, the chemical may cause fire, particularly if the clothing is soiled.
Contact with moderate concentrations of hydrogen peroxide will cause whitening of
the skin and stinging sensations. The whitening is due to the formation of gas bubbles
in the epidermal layer of the skin. The stinging, in most cases, subsides quickly after
thorough washing, and the skin gradually returns to normal without any damage.
Highly concentrated hydrogen peroxide can cause blistering if left on skin surfaces for
any length of time.

11.7 Accidental Swallowing
Hydrogen peroxide, a mild disinfectant, is useful in counteracting various
microorganisms. Because of their antiseptic action, dilute hydrogen peroxide
solutions (3% or less) are frequently used to treat open wounds and can be used as a
gargle or mouthwash. However, contact or concentrated solutions (over 3%) with the
members of the mouth is to be avoided. Under no circumstances should hydrogen
peroxide be taken internally. If hydrogen peroxide is swallowed, drink water
immediately to dilute, and contact a physician but do not attempt to cause vomiting.
In using hydrogen peroxide, safety should be first in the minds of everyone, and as
with any other chemical, initial steps should be taken to familiarize all personnel with
its safe and proper handling. Acceptance of hydrogen peroxide in a wide variety of
industrial applications is a reflection of its simplicity in use.
Maximum safety in handling hydrogen peroxide is assured through the use of proper
materials of construction, recognition of the need for venting in storage, and overall
avoidance of contamination. The oxygen and water by-products of decomposition are
innocuous, but splashing, inhaling vapor, and ingesting hydrogen peroxide must be
avoided. If by unusual circumstances an accident should take place, flushing with
large quantities of plain water is the simple corrective action needed. By adhering to
straight-forward common sense procedures, every aspect of your operation will be
aimed toward safety and a clean environment.
HYDROGEN PEROXIDE
61

CHAPTER 12: PLANT LAYOUT



Following Factor should be considered in planning layout:

(1) New site development or addition to a previously development site.

(2) Future expansion.

(3) Economic distribution of service-water, process-steam, power and gas.

(4) Weather consideration, are they amenable to outdoor construction.

(5) Safety consideration, possible hazards of fire, explosion and flumes.

(6) Building code requirement.

(7) Sensible use of floor and elevation space.

12.1 Storage
Regulations vary, but low concentrations, such as 2.5% are widely available and legal
to buy for medical use. Small quantities of many different concentrations and grades
can be legally stored and used with few regulations.
Hydrogen peroxide should be stored in a container made from a material that it
doesn't react with and doesn't catalyze its decomposition. Numerous materials and
processes are available, some stainless steels, many plastics, glasses and some
aluminum alloys are compatible.
Peroxide is a strong oxidant and should be stored away from fuel sources and sources
of catalytic contamination. Apart from obvious fire risks, peroxide vapor can react
with hydrocarbons and alcohols to form contact explosives. Because oxygen is
formed during the natural decomposition of the peroxide, the resulting increase in
pressure can cause a container (e.g. made of glass) to shatter. Peroxide should be kept
cool, as peroxide vapor can detonate above 70 C. Deaths have occurred from storage
in inadequately labeled containers due to its apparent similarity to water.
CONCLUSION HYDROGEN PEROXIDE
86

PARKING
AREA
SECURITY
OFFICE
POWER
TRANMISSION
PRODUCT
PACKAGE
AND
STORAGE
ADMINISTRATION
DEPARTMENT
CANTEEN SHOP
R & D
LABORATORY
UTILITY AREA
PROCESSING AREA
EFFLUENT
TREATMENT
PLANT
FUTURE EXPANSION
RAW MATERIAL
STORAGE AREA
FIRE AND
SAFETY
DEPARTMENT
PLANTATION
AREA
PLANTATION
AREA
MAINTAINENCE



CONCLUSION HYDROGEN PEROXIDE
87

12.2 Factor Affecting the Final Selection

- Raw material

Ample supply of material should be available regularly as per requirements.
This reduces the transportation & hence reduce produce the transportation & hence
reduce production cost.

- Market

Plant should be located in center of market or nearer to the market which helps in
studying market property, reduces delays in supply & also reduces transportation cost.

- Power & fuel supply

Electricity & fuel should be available of at the site regularly & cheaply otherwise
process ability may cease.

- Water supply

Plant is located where sufficient water is available.

- Climates

Weather condition considerably affects the plant location temperature & humidity
shall be favorable.

12.3 Specific Factor

- Transportation

Railway & roads are common means of transportation. So they must be available for
raw materials for product transportation.

- Water & Waste Disposal

Plant site should have adequate & proper facility for correct water & waste disposal.



CONCLUSION HYDROGEN PEROXIDE
88

- Labor

Availability of skilled labor with constant supply & reasonable pay rate should be
considered while selecting the site.

- Taxes & legal phases

State & local tax rates & property, income, unemployment insurance zoning
ordinance, building codes etc. have major influence.

- Site characteristic

The site should facilities, soil; structure should be good for building & easily available
for future expansion of plant.

- Miscellaneous

Various more factors like community around plant site, fire highly facility, advance
library & training center, housing cost, etc. also affect the location.

Thus, considering all above major factors & nature of our plant we can select the best
suitable place for our plant near vadodara.

12.4 Utilities

The Synthesis Loop and peroxide processing stages are dependent on a number of
ancillary processes.

- Hydrogen Plant

This plant processes natural gas through a steam reforming stage and subsequent high
temperature shift catalytic stage to produce high purity hydrogen gas. The gas is finally
purified in a pressure swing absorber before being used by the hydrogenator Details of
this process can be found in the manufacture of methanol.

- Demineralised Water

High purity water is used to feed the extractor, concentrator as well as the
package boiler. Conventional degassing followed by cation and anion exchange beds is
used to purify town water for use in the peroxide process.
CONCLUSION HYDROGEN PEROXIDE
89


- Package Boiler

A small boiler generates steam for use in concentrating crude peroxide from 25-35% to
35-70%.

- Waste Gas System

The oxidiser can produce an exit gas containing trace levels of solvents. The solvent-
entrained gas is fed to a bed of activated carbon where the solvents are absorbed onto the
carbon. The activated carbon is purged with nitrogen gas and the solvent is stripped off
and recovered for reuse in the synthesis loop.

- Calciner Systems

A calciner is used to regenerate spent catalyst on a periodic basis. The catalyst is
removed from the regenerators, washed and then roasted to remove any other organics
that might be present. These organics, if not removed, will block the catalytic sites on the
catalyst and lower its activity.

- Fire System

The hydrogen peroxide manufacturing process uses natural gas, hydrogen and organic
solvents, all of which are highly flammable. The site is equipped with a delug system
with foam injection. In addition, the local fire brigade has been provided with a foam
tender.

- Working Solution Regeneration

Hydrogenation generates not only peroxide-producing anthrahydroquinones but also
some by-products. These by-products include anthraquinone species that can be
converted back to useful quinones by regeneration.

During regeneration process, aside-stream of working solution is fed through a bed of
dehydrogenation catalyst. The regeneration converts epoxidised anthraquinones and
tetrahydroanthraquinones to their corresponding anthraquinones.




CONCLUSION HYDROGEN PEROXIDE
90

CHAPTER 13: COST ESTIMATION AND PROFITABILITY



[1] Direct Cost = (A+B+C+D+E)

Now, A= Equipment
B=Installation
C= Instrumentation
D=Piping
E=Electrical.


Now, (1) Equipment Costs

Sr
No.
Name of Unit Quantity Cost
(1) Hydrogenation Unit 1 500000
(2) Oxidation Unit 1 800000
(3) Extraction Unit 1 700000
(4) Catalyst particle barrier 1 300000
(5) Degassing unit 1 200000
(6) Air supply unit 1 600000
(7) Water storage tank 1 550000
(8) Working solution st. tank 1 550000
(9) Hydrogen peroxide st. tank 1 600000
(10) Hydrogen supply unit 1 600000
(11) Pumps As required 200000
TOTAL (X) Rs. 5600000/-





(2) Installation cost (including installation and painting) = 30% of X
= Rs. 1680000/-


(3) Instrumentation and control installed = 20% of X
= Rs. 1120000/-


(4) Piping Installed = 25% of X
= Rs. 1400000/-


(5) Building costs = 20% of X
= Rs. 1120000/-

CONCLUSION HYDROGEN PEROXIDE
91

(6) Service facilities and Ward improvement = 50% of X
= Rs. 2800000/-
(7) Land = 50% of X
= Rs. 840
Total Cost = Rs. 14560000/-


[2] Indirect Cost = (A+B+C)


A) Engineers and Supervisor = 30% of X
=Rs. 1680000/-

B) Construction & Expenses = 34% of X
=Rs. 1904000/-

C) Contingency = 10% of X
= Rs. 560000/-

Total Cost = Rs. 4144000/-


[3] Fixed Capital Investment = Direct Cost + Indirect Cost
= 14560000 + 4144000
= Rs. 18704000/-


[4]Working Capital = 10% OF FCI
= Rs. 1870400/-


[5] Total Capital = Fixed Capital + Working Capital
= 18704000 + 1870400
= Rs. 20574400


[6] Operating Suppliers = 15% Of Cost Of Maintenance And Repair
= Rs. 840000/-


[7] Laboratory Charges = 15% Of X
= Rs. 840000/-


(A) Fixed Charges

(1) Depreciation:
= 10% of fixed capital investment
= 0.10 x 18704000
= Rs. 1870400/-
CONCLUSION HYDROGEN PEROXIDE
92

(2) Local Taxes:
= 3% of fixed capital investment
= 0.03 x 18704000
= Rs. 561120/-

(3) Insurance:
= 1% of fixed capital investment
= Rs. 187040/-
(4) Rent :
= 8% of building
= 0.08 x 1120000
= Rs. 89600/-

Fixed Charges (1+2+3+4) = Rs. 2708160

(B) Plant Overhead Costs
= 10% of total product cost=0.10y
= 0.10 x 188591200
= Rs.18859120 /-


(C) General Expenses = A+B+C+D
= 0.02Y + 1440208

A = Administration costs
= 4%Y

B = Distribution and selling cost
= 11%Y

C = Research and development costs
= 5%Y

D = financing (interest)
= 7% of total capital investment
= 0.07 x 20574400
= Rs. 1440208/-

(D) Mfg. Cost = (A+B+C) = 0.66Y + 24962560

A = Raw material cost
= 40%Y

B = Electricity & Utility Cost
= 20%Y

C = House keeping Cost
= 6%


CONCLUSION HYDROGEN PEROXIDE
93

(E) Total Product Cost = Mfg. Cost + General Expenses
= (24962560 + 0.66Y) + (0.20Y + 1440208)
Y = 26402768 + 0.86Y
Y = Rs. 188591200/-


- Sales: 10000 TPA (40 Rs./Kg)

Selling = 400000000/-
Commission to asset = 20000000/-
Sales = 20000000/-

Total = Rs.440000000/-

- Profitability = Gross Income Total Production Capacity

= 440000000 188591200
= Rs. 251408800/-

Less 60% income tax = Rs. 150845280/-

- Profit (Net) = 251408800 150845280

= Rs. 100563520/-


- Payout period = Fixed capital investment
------------------------------------------------------
(Net Profit + Depreciation)

= 18704000
-------------------------------------------------------
(100563520 + 1870400)

= 0.1826 years

= 2.5 Month

- % Rate of Return (before taxes)=
nt alInvestme Totalcapit
ngx GrossEarni 100


=
20574400
100 440000000x


= 2138.57%



CONCLUSION HYDROGEN PEROXIDE
94

- % Rate of Return (After taxes)=
nt alInvestme totalCapit
ftertax netprofita 100 *


=
20574400
100 100563520x


= 488.77%



- Break Even Point

Direct product cost (Rs/ kg) = Annual Production cost (Rs) Sales Price (Rs/ kg)
Annual sales (Rs)
= 188591200 40 .
440000000
= 17.14Rs/ kg

kg/ annum (n) required for break even point
= Fixed charges + General expense .
Sales Price (Rs/ kg) - Direct product cost (Rs/
kg)
= 27670720.
40- 17.14
= 1210442.69 kg/ annum

Annual capacity of the plant is 10000000 kg.

Break even point = kg/ annum (n) required for break even point 100
Annual production
= 1210442.69 100
10000000
= 12.10 % of capacity.











CONCLUSION HYDROGEN PEROXIDE
95

CONCLUSION


In this project, I have used such as materials quinone, hydrogen, and oxygen for the
manufacture of the hydrogen peroxide. These are widely used in the industries & are
the most economical than the other processes.

Hydrogen peroxide is a much weaker base than water in nature.

Mol wt. is 34 kg/kg mole.

The use of hydrogen peroxide is in the Bleaching wood pulp, Detoxification of cyanide
tailings, Bleaching of cotton fabrics, Bleaching of wool, Measuring dissolved oxygen,
Destroying soluble cyanides, sulfides and phenols, Aseptic packaging of milk and fruit
juice

Warning:-

1. Physiologically, a prominent factor in process safety is to prevent hydrogen
peroxide from splashing on personnel, particularly on sensitive membrane areas such
as eyes.
2. Hazardous reactions ranging from ignition to explosion have been reported with
alcohols, ketones, carboxylic acids (particularly acetic acid), amines and phosphorus.
3. Hydrogen peroxide vapors can form sensitive contact explosives with hydrocarbons
such as greases.

Material of construction for process is Austenitic stainless steels and certain grades of
aluminum are used almost universally for vessels, piping, valves, and pumps.
Stainless steel grades 304 and 316 are used widely. Aluminum grades 5652, 1060, and
1100 are satisfactory but less used in plants built in recent years. Aluminums ability
to self-passivate with an oxide coating is a property which commends the metal
particularly to peroxide handling.
The IUPAC name of hydrogen peroxide: Dihydrogen dioxide.
HYDROGEN PEROXIDE
96

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